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Three-dimensional hierarchical Co(OH)F nanosheet arrays decorated by single-atom Ru for boosting oxygen evolution reaction

单原子Ru修饰的三维多级Co(OH)F纳米片阵列高效催化析氧反应

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Abstract

Electronic coupling with the support plays a crucial role in boosting the intrinsic catalytic activity of a single-atom catalyst. Herein, the three-dimensional (3D) hierarchical Co(OH)F nanosheet arrays modified by singleatom Ru (SA-Ru/Co(OH)F) are prepared by a facile one-step hydrothermal method under mild conditions, which exhibit excellent activity with an overpotential of 200 and 326 mV at 10 and 500 mA cm−2, respectively, as well as robust stability for oxygen evolution reaction (OER) in 1.0 mol L−1 KOH electrolyte. The study of electronic structures and surface chemical states before and after OER testing reveals that the strong electronic coupling between single-atom Ru and Co(OH)F induces the charge redistribution in SA-Ru/Co(OH)F and suppresses the excessive oxidation of Ru into higher valence state (more than +4) under high OER potential. This work provides a strategy to stabilize single-atom Ru by Co(OH)F that can enhance the activity and durability for OER under large current densities.

摘要

单原子与基底之间的电子耦合在提升单原子催化剂的本征 催化活性方面起到至关重要的作用. 本文通过一步水热法在温和 条件下制备了单原子Ru修饰的三维多级Co(OH)F纳米片阵列催化 剂. 该催化剂在1 mol L−1 KOH电解液中展现出高的电催化析氧反 应活性和稳定性, 在10和500 mA cm−2的电流密度下分别表现出 200和326 mV的过电位. 通过对催化剂析氧反应前后的电子结构和 表面化学态的研究发现, 单原子Ru和Co(OH)F之间强烈的电子耦 合诱导体系电荷重新分布, 并抑制了Ru在高的OER电势下被过度 氧化为过高的价态(大于+4价). 本工作提供了一个通过羟基氟化钴 稳定单原子Ru, 以提高大电流下析氧反应的活性和稳定性的策略.

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Acknowledgements

This work was supported by Taishan Scholar Program of Shandong Province, China (ts201712045), Shandong Provincial Key Research and Development Program (2019GGX102069), the Natural Science Foundation of Shandong Province of China (ZR2018BB008), Doctoral Found of Qingdao University of Science and Technology (0100229001 and 010029081) and 2019 Research Funds of Ulsan National Institute of Science and Technology, South Korea (1.190002.01).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory Base of Eco-Chemical Engineering, College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao, 266042, China

    Shizheng Zhou  (周士正), Qing Qin  (秦清), Chuang Li  (李创) & Xien Liu  (刘希恩)

  2. Department of Energy Engineering, Department of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan, 44919, South Korea

    Haeseong Jang & Jaephil Cho

  3. Department of Chemistry, City University of Hong Kong, Hong Kong, China

    Zijian Li  (李子健)

  4. Beamline Research Division, Pohang Accelerator Laboratory (PAL), Pohang, 37673, South Korea

    Min Gyu Kim

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  1. Shizheng Zhou  (周士正)
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Contributions

Liu X and Cho J proposed the research and designed the experiments; Qin Q and Liu X performed the analysis and wrote the manuscript; Zhou S, Li Z and Li C conducted material synthesis and electrochemical measurements; Jang H and Kim MG conducted XAS and other physical characterizations. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Qing Qin  (秦清), Xien Liu  (刘希恩) or Jaephil Cho.

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Experimental details and supporting data are available in the online version of the paper.

Conflict of interest

The authors declare that they have no conflict of interest.

Shizheng Zhou is currently pursuing his PhD degree under the supervision of Prof. Xien Liu at Qingdao University of Science and Technology. His current research interests focus on the design and syntheses of noble metal-based electrocatalysts for HER and OER.

Qing Qin received her PhD degree in 2017 from Nankai University. Now she is a professor of Qingdao University of Science and Technology. Her current research interests focus on the design and syntheses of noble metal- and nonnoble metal-based electrocatalysts for overall water splitting and Zn-air batteries.

Xien Liu received his PhD degree from Dalian University of Technology. He is currently a professor of Qingdao University of Science and Technology. His research interests focus on the design of electrocatalysts for electrochemical energy conversion and storage devices.

Jaephil Cho is a professor and head of the School of Energy and Chemical Engineering at UNIST (Korea). He is a director of the Green Energy Materials Developed Center (granted by the Ministry of Trade, Industry, and Energy, South Korea) and Samsung SDI-UNIST Future Battery Research Center. His current research mainly focuses on Li-ion and metal-air batteries and redox flow batteries for energy storage.

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Zhou, S., Jang, H., Qin, Q. et al. Three-dimensional hierarchical Co(OH)F nanosheet arrays decorated by single-atom Ru for boosting oxygen evolution reaction. Sci. China Mater. 64, 1408–1417 (2021). https://doi.org/10.1007/s40843-020-1536-6

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